CN103641077B - A kind of circulation utilization method of sodium hydrosulfite wastewater - Google Patents

A kind of circulation utilization method of sodium hydrosulfite wastewater Download PDF

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Publication number
CN103641077B
CN103641077B CN201310690384.XA CN201310690384A CN103641077B CN 103641077 B CN103641077 B CN 103641077B CN 201310690384 A CN201310690384 A CN 201310690384A CN 103641077 B CN103641077 B CN 103641077B
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sodium
water
raffinate
sodium hydrosulfite
reaction
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CN103641077A (en
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赵伟明
叶华明
陈建忠
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ZHEJIANG JIACHENG CHEMICAL CO Ltd
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ZHEJIANG JIACHENG CHEMICAL CO Ltd
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Abstract

The invention provides a kind of Application way of sodium hydrosulfite wastewater, comprise: after sodium formiate, methyl alcohol, water, Sodium Pyrosulfite, sulfurous gas raw material configure by (1) in proportion, react 3 ~ 6 hours, reaction system to be carried out after reaction terminates filtering, wash and obtain sodium hydrosulfite wastewater and filter cake, namely filtration cakes torrefaction obtains vat powder; (2) described sodium hydrosulfite wastewater alkali lye is neutralized to pH8 ~ 11, obtains S-WAT after filtration, filtrate is reclaimed methyl alcohol and is back to use in step (1), residue raffinate; (3) after described raffinate leaves standstill, the turbid liquid of sub-cloud is divided to be back to use in step (2), remaining supernatant liquid is after thickening, the sodium formiate obtained is back in step (1), catalyzer is added in the distilled water obtained, obtain low COD waste water after reaction, described low COD waste water is for the production of dispersion agent or water reducer.Method provided by the invention can not affect the vat powder quality of gained, and the performance index of the dispersion agent prepared or water reducer do not affect.

Description

A kind of circulation utilization method of sodium hydrosulfite wastewater
Technical field
The present invention relates to the comprehensive utilization of byproduct and waste water in Chemical Manufacture, in particular, relate to a kind of circulation utilization method of sodium hydrosulfite wastewater.
Background technology
Sodium hydrosulfite wastewater process, existing treatment process is all generally that sodium hydrosulfite wastewater is direct and other Wastewater Concentrated, also have part to use in other operations to go, but certain impact can be produced, a kind ofly produce vat powder as Chinese patent 200710164628.5 discloses and utilize the method for sodium hydrosulfite wastewater lignin co-production sodium sulfonate, the method mainly utilizes the S-WAT in vat powder raffinate and sodium hydroxide etc. to carry out reacting to produce sodium lignosulfonate with xylogen.
Because of the expansion of current vat powder output, sodium hydrosulfite wastewater process has become extremely urgent thing, how reasonably to utilize sodium hydrosulfite wastewater, not to environment, has constrained the output of vat powder.
Summary of the invention
For deficiency of the prior art, the object of the present invention is to provide a kind of circulation utilization method of sodium hydrosulfite wastewater, step is as follows:
(1) wastewater source: will comprise after the raw materials such as sodium formiate, methyl alcohol, water, Sodium Pyrosulfite, sulfurous gas configure by a certain percentage; react 3 ~ 6 hours under nitrogen protection; after reaction terminates reaction system carried out filtering, wash and obtain sodium hydrosulfite wastewater (being also called mother liquor) and filter cake, namely filtration cakes torrefaction is obtained vat powder.
(2) described sodium hydrosulfite wastewater sodium hydroxide is neutralized to pH8 ~ 11, the solid obtained after filtration is S-WAT (by weight percentage, gained S-WAT content is about 90%, normal commercial use can be carried out), by the filtrate Distillation recovery methyl alcohol obtained, and the methyl alcohol of recovery is back to use in step (1), residue raffinate.
(3) after described raffinate leaves standstill, the turbid liquid of sub-cloud is divided to be back to use in step (2), remaining supernatant liquid (carries out thickening preferably by distillation) again after thickening, residue sodium formiate, be back to by this sodium formiate in step (1), concentrated water vapor, after condensation, obtains the water through distillation, after this adds catalyst reaction in the water of distillation, obtain low COD waste water, described low COD waste water is for the production of dispersion agent or water reducer.
In aforesaid method, the production of the vat powder in step (1) can be carried out according to this area ordinary method, the production of vat powder and identical in Chinese patent 200710164628.5 in the application.Such as, the mixture that sodium formiate can be dissolved in first alcohol and water makes solution A, by Sodium Pyrosulfite and methyl alcohol and mixed; then pass into sulfurous gas and make solution B; by solution A and solution B mixing, pass into nitrogen as protection gas, 81-86 DEG C of insulation reaction 3 ~ 6 hours simultaneously.
In step (1), the ratio of described raw material sodium formiate, methyl alcohol, water, Sodium Pyrosulfite, sulfurous gas can be such as 1000kg:800 ~ 1200kg:0.2 ~ 0.4m 3: 800 ~ 1000kg:0.2 ~ 0.4m 3.
In aforesaid method, in step (3), after described raffinate leaves standstill, point turbid liquid of lower floor gone accounts for 70 ~ 90% of described raffinate cumulative volume, and remaining supernatant liquid part accounts for 30 ~ 10% of described raffinate cumulative volume.
In aforesaid method, in step (3), in described low COD waste water, the concentration of COD is 10000 ~ 20000mg/L.
In aforesaid method, in step (3), described catalyzer is not specific especially, as long as meet required catalytic performance, such as described catalyzer can be sodium chlorate.The consumption of described catalyzer is 1 ~ 5% of the volume of the described water through distillation.
By aforesaid method continuous seepage, the vat powder quality of gained can not be affected.
By described low COD waste water for the production of dispersion agent or water reducer, the performance index of gained dispersion agent or water reducer do not affect.
Existing vat powder production technique, the wastewater flow rate produced in production is larger, and wastewater treatment difficulty is larger, the methods such as the process of general employing Fenton reagent, charcoal absorption decolouring, and processing cost is higher; After adopting the present invention, the whole recycle of sodium hydrosulfite wastewater, wastewater zero discharge, and waste water comprehensive treating process is fairly simple, production is implemented easily, equipment requirements is lower, and more topmost be the outlet solving sodium hydrosulfite wastewater, solve the output bottleneck problem of vat powder.
Accompanying drawing explanation
Fig. 1 is the production technological process of sodium hydrosulfite wastewater recycle of the present invention.
Embodiment
Below by embodiment, the invention will be further described, but should to understand these embodiments be only illustrative, and the present invention is not limited to this.
In following examples, the conventional medication such as sodium formiate, methyl alcohol, washing oil, liquid caustic soda and reagent are industrial goods.
Embodiment 1
See Fig. 1, after being configured by a certain percentage by vat powder synthesis material, (ratio of sodium formiate, methyl alcohol, water, Sodium Pyrosulfite, sulfurous gas is 1000kg:800kg:0.2m 3: 800kg:0.4m 3), react 6 hours under the protection of nitrogen, after reaction terminates, filter, washing, obtains filter cake and sodium hydrosulfite wastewater 3m 3; Filter cake obtains sodium hydrosulfite finished product 1900kg after drying; Sodium hydrosulfite wastewater is through 30% sodium hydroxide solution 0.3m 3after being adjusted to about pH10, filtering and obtain S-WAT solid 900kg, this part S-WAT can be used as industrial S-WAT and uses, and content is about 90%; Filtrate after filtration is by Distillation recovery methyl alcohol 1.8m 3, residue raffinate 0.9m 3, after raffinate leaves standstill, during the turbid liquid of lower floor 80% is back to use and in operation, the clear liquid on remaining upper strata 20% is by after thickening, and residue is sodium formiate 100kg, synthesizes for vat powder; The water vapour obtained after concentrated obtains the water through distillation by condensation, 30% sodium chlorate aqueous solution (4kg) reaction is added in the water through distillation, obtain low COD waste water (COD concentration is 12000mg/L), this low COD waste water, for the production of dispersion agent or water reducer, is produced for the Dispersant MF of 98% sulfuric acid sulfonation.
Add 2000kg washing oil in a kettle., add 2000kg98% sulfuric acid, be warmed up to 150 DEG C and carry out sulfonation reaction 4 hours, add the water of 800kg after cooling to 110 DEG C, then add 900kg37% industrial formol, be warming up to 100 DEG C of condensation reactions 4 hours, in and add the above-mentioned low COD waste water of 2000kg in still, drop into lime 100kg, the material putting into above-mentioned condensation good is a collection of, neutral to pH with liquid caustic soda (30%NaOH solution) neutralization, obtain MF slurry.Gained MF property indices all meets the requirements.
Above-mentioned low COD waste water is equally applicable to dispersion agent and the water reducer production technique of oleum sulfonation.
Embodiment 2
See Fig. 1, after being configured by a certain percentage by vat powder synthesis material, (ratio of sodium formiate, methyl alcohol, water, Sodium Pyrosulfite, sulfurous gas is 1000kg:1200kg:0.4m 3: 1000kg:0.2m 3), react 4 hours under the protection of nitrogen, after reaction terminates, filter, washing, obtains filter cake and sodium hydrosulfite wastewater 4m 3; Filter cake obtains sodium hydrosulfite finished product 2000kg after drying; Sodium hydrosulfite wastewater is through 30% sodium hydroxide solution 0.4m 3after being adjusted to about pH10, filtering and obtain S-WAT solid 1000kg, this part S-WAT can be used as industrial S-WAT and uses, and content is about 90%; Filtrate after filtration is by Distillation recovery methyl alcohol 1.9m 3, residue raffinate 1m 3, after raffinate leaves standstill, during the turbid liquid of lower floor 80% is back to use and in operation, the clear liquid on remaining upper strata 20% is by after thickening, and residue is sodium formiate 200kg, synthesizes for vat powder; The water vapour obtained after concentrated obtains the water through distillation by condensation, 30% sodium chlorate aqueous solution (6kg) reaction is added in the water through distillation, obtain low COD waste water (COD concentration is 12000mg/L), this low COD waste water, for the production of dispersion agent or water reducer, is produced for the Dispersant MF of 98% sulfuric acid sulfonation.
Add 2000kg washing oil in a kettle., add 2000kg98% sulfuric acid, be warmed up to 150 DEG C and carry out sulfonation reaction 4 hours, add the water of 800kg after cooling to 110 DEG C, then add 900kg37% industrial formol, be warming up to 100 DEG C of condensation reactions 4 hours, in and add the above-mentioned low COD waste water of 2000kg in still, drop into lime 100kg, the material putting into above-mentioned condensation good is a collection of, neutral to pH with liquid caustic soda (32%NaOH solution) neutralization, obtain MF slurry.Gained MF property indices all meets the requirements.
Above-mentioned low COD waste water is equally applicable to dispersion agent and the water reducer production technique of oleum sulfonation.

Claims (2)

1. a circulation utilization method for sodium hydrosulfite wastewater, comprises step as follows:
(1) by comprise sodium formiate, methyl alcohol, water, Sodium Pyrosulfite, sulfurous gas raw material configure in proportion after, react 3 ~ 6 hours under nitrogen protection, reaction system to be carried out after reaction terminates filtering, wash and obtain sodium hydrosulfite wastewater and filter cake, namely described filtration cakes torrefaction obtains vat powder;
(2) described sodium hydrosulfite wastewater sodium hydroxide is neutralized to pH8 ~ 11, the solid obtained after filtration is S-WAT, by the filtrate Distillation recovery methyl alcohol obtained, is back to use by the methyl alcohol of recovery in step (1), residue raffinate;
(3) after described raffinate being left standstill, the turbid liquid of sub-cloud is divided to be back to use in step (2), remaining supernatant liquid is after thickening, the sodium formiate obtained is back in step (1), and concentrated water vapor, after condensation, obtains the water through distillation, in the water of distillation, catalyzer is added described, obtain low COD waste water after reaction, described low COD waste water is for the production of dispersion agent or water reducer, and in described low COD waste water, COD concentration is 10000 ~ 20000mg/L; In step (3), after described raffinate leaves standstill, point turbid liquid of lower floor gone accounts for 70 ~ 90% of described raffinate cumulative volume, and remaining supernatant liquid part accounts for 30 ~ 10% of described raffinate cumulative volume.
2. method according to claim 1, is characterized in that, in step (3), catalyzer is the sodium chlorate aqueous solution of 30%, and its consumption is 1 ~ 5% of the volume of the described water through distillation.
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CN104261434A (en) * 2014-10-16 2015-01-07 烟台市金河保险粉厂有限公司 Method for producing anhydrous sodium sulfite by utilizing crude methanol rectification residual liquid in production process of sodium hydrosulfite
CN104478159B (en) * 2014-11-20 2016-01-06 湘潭大学 The method of a kind of sodium formate method sodium hydrosulfite wastewater process
CN105016312B (en) * 2015-07-08 2017-03-01 湖南龙盛环保有限公司 A kind of method that in sodium hydrosulfite production, sulfur containing waste material recycles
CN105585192B (en) * 2015-12-25 2018-03-09 石家庄杰克化工有限公司 A kind of method of wastewater treatment of 4,6 dihydroxy-pyrimidine production
CN106186519A (en) * 2016-07-22 2016-12-07 浙江嘉成化工有限公司 A kind of processing method of sodium hydrosulfite wastewater
CN109053422A (en) * 2018-09-21 2018-12-21 浙江嘉成化工有限公司 The processing method and equipment of insurance powder waste liquid in sodium hydrosulfite production process

Citations (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN101081715A (en) * 2007-04-06 2007-12-05 广东中成化工股份有限公司 Method for treating residual liquid after mother liquor distillation methanol recovery during production of sodium sulphoxylate by sodium formate process
CN101214930A (en) * 2007-12-26 2008-07-09 浙江闰土股份有限公司 Method for producing sodium hydrosulfite and coproducing lignin sodium sulphonate from residual liquid thereof

Patent Citations (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN101081715A (en) * 2007-04-06 2007-12-05 广东中成化工股份有限公司 Method for treating residual liquid after mother liquor distillation methanol recovery during production of sodium sulphoxylate by sodium formate process
CN101214930A (en) * 2007-12-26 2008-07-09 浙江闰土股份有限公司 Method for producing sodium hydrosulfite and coproducing lignin sodium sulphonate from residual liquid thereof

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